This application is directed to the reduction of very minute quantities of cyclopentadiene (hereinafter referred to as CPD) from hydrocarbon streams. It has been found that a number of hydrocarbon streams, particularly those containing mixtures of C-5 saturated hydrocarbons and unsaturated hydrocarbons containing, for instance, isoprene, pentane, pentene and CPD are of commercial value. However, CPD or dicyclopentadiene have an inhibiting effect on the subsequent polymerization of isoprene to cis-1, 4-polyisoprene. In the polymerization reaction, the Ziegler-Natta catalyst tends to be poisoned by the CPD.
To a large extent, many of the undesirable compounds can be removed by means of distillation of the hydrocarbon stream. However, because the boiling points of the C-5 hydrocarbon are very close, it is necessary to carry out distillation in columns having a large number of trays in order to achieve an adequate degree of separation. Such a distillation has been found to be technically and economically unattractive.
One known method for removal of CPD consists in binding CPD by carbonyl compounds such as benzaldehyde, salicylaldehyde, acetophenone, cyclopentanone in the presence of alkali metal alcoholates with the formation of the respective fulvenes. A decontaminated hydrocarbon is further treated with sodium bisulfite and water to remove said carbonyl compound and the fulvenes are distilled off. The disadvantage of this method is that the alkali metal alcoholate used therein as a catalyst is expensive and requires thorough dessication of the decontaminated hydrocarbon, the consumption of the catalyst being important since it is decomposed by water released during the binding of cyclopentadiene. Furthermore, the carbonyl compounds used are capable of being polymerized under the conditions of hydrocarbons decontamination resulting in clogging of equipment and excluding the possibility of stable operational conditions.
It is also possible to remove CPD from hydrocarbon mixtures by thermal dimerization and separation of the dimerized product from other hydrocarbons, such as isoprene, by means of distillation. However, dimerization takes a long time to decrease the amount of CPD to the very low concentrations permissible for isoprene polymerization, and still requires separation by distillation. Moreover, the resultant CPD dimers are of little commercial value.
Another known method for the removal of 1,3-CPD from an isoprene stream is by the addition of a solution of maleic anhydride in dimethyl formamide. The solution has a weight ratio of maleic anhydride to dimethyl formamide of about 2:1. This solution is added to the isoprene stream to give a 1.6 percent solution by weight which is allowed to react for 11/2 hours without agitation. The CPD-maleic anhydride adduct and unreacted maleic anhydride are then removed from the isoprene stream by use of a caustic scrubber such as aqueous sodium hydroxide.
One known method for the removal of CPD from a hydrocarbon mixture containing isoprene consists of contacting the isoprene mixture with dehydrated molecular sieve material containing at least one alkali metal and having a pore diameter of more than 0.6 nanometers.
Another known method of decontaminating hydrocarbons used as solvents and monomers in the production of synthetic rubber by stereospecific polymerization from CPD which is present in the amount of 0.001-0.5 percent by weight of said hydrocarbons, comprises treating a mixture of said hydrocarbons and CPD with acyclic ketone having from 6 to 12 carbon atoms at a 10-2000 times stoichiometric-excess of said ketone with respect to CPD in the presence of a catalyst selected from the group consisting of alkali metal hydroxide or an anionic exchange resin in the (OH--) form thus obtaining a fulvene, said treatment taking place in the presence of 50 to 60 percent of a fulvene by weight of the hydrocarbons being decontaminated, said fulvene having been recycled together with unreacted ketone from a previous distillation of decontaminated hydrocarbons; and distilling off the decontaminated hydrocarbons containing not more than 0.0001 percent by weight of CPD. The disadvantage of this method is the required distillation of the hydrocarbon mixture.
Still another known process for purifying isoprene from mixtures thereof with carbonyl compounds and CPD produced by the catalytic decomposition of dimethyldioxane consists of the steps of passing the isoprene mixture at a temperature of from 40.degree. to 70.degree. C. through a bed of solid product which comprises an anion exchange resin or alkali, and subjecting said isoprene mixture to fractionation with at least 50 theoretical plates and a reflux ratio of at least 3, recycling 20 to 80 weight percent of said purified isoprene following close fractionation for admixture with the starting isoprene to be purified.